CN108654695A - 吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用 - Google Patents
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用 Download PDFInfo
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- CN108654695A CN108654695A CN201710197166.0A CN201710197166A CN108654695A CN 108654695 A CN108654695 A CN 108654695A CN 201710197166 A CN201710197166 A CN 201710197166A CN 108654695 A CN108654695 A CN 108654695A
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- catalyst
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- oxazolidine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 26
- 150000002475 indoles Chemical class 0.000 title claims abstract description 25
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005686 cross metathesis reaction Methods 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- -1 diallyl diethyl malonate Chemical compound 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- 239000001128 3-phenylprop-2-enyl benzoate Substances 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 1
- UARVBDPGNUHYQT-JXMROGBWSA-N Cinnamyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC\C=C\C1=CC=CC=C1 UARVBDPGNUHYQT-JXMROGBWSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
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- UARVBDPGNUHYQT-UHFFFAOYSA-N benzoic acid cinnamyl ester Natural products C=1C=CC=CC=1C(=O)OCC=CC1=CC=CC=C1 UARVBDPGNUHYQT-UHFFFAOYSA-N 0.000 description 1
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- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
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- C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
- C07D313/08—Seven-membered rings condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开了吲哚[3,2‑a]恶唑烷标记的钌卡宾催化剂及制备方法及应用,吲哚[3,2‑a]恶唑烷标记的钌卡宾催化剂,其特征是用式(II)所示:
Description
技术领域
本发明属过渡金属有机催化剂领域,涉及一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用。
背景技术
为了解决均相烯烃复分解催化剂在反应完成后难以从混合物中分离出来的问题,近年来人们合成了一系列离子标记,氟标记以及氧化还原开关标记的可回收钌烯烃复分解催化剂[1-6]。此外,人们还有利用硅基材料、聚合物和磁性纳米粒子制备了负载型钌催化剂[2-9]。
这些系统需要昂贵的离子液体作为载体材料,导致异质性,并因此降低随后反应中的反应速率。此外,这些方法常常在再循环的催化剂中产生杂质,例如已分解的催化剂,这可能加速未来反应中的催化剂分解等诸如此类问题。
发明内容
本发明的目的是为了克服现有技术的不足,提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂。
本发明的第二个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法。
本发明的第三个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂催化闭环和交叉复分解反应中的应用。
本发明的第四个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的回收方法。
本发明的技术方案概述如下:
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂,是用式(II)所示:
上述吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法,包括如下步骤:
氮气保护下,将Grubbs II催化剂(III)、氯化亚铜和化合物(I)溶于二氯甲烷中,在搅拌下,加热回流25-35min,降温至室温,旋干,过色谱硅胶柱,向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质,再加入二氯甲烷做洗脱得到吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II),反应式如下:
所述Grubbs II催化剂的结构见(III):
优选地,Grubbs II催化剂,氯化亚铜和化合物(I)的摩尔比为1:1:1.25
上述吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中的应用。
本发明的优点:
本发明的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中催化效率高,催化剂回收后可以重复使用,降低了成本,减少了污染。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
化合物(I)(吲哚[3,2-a]恶唑烷配体),用式(I)所示:
实施例1
化合物I的合成:
1)在圆底烧瓶中氮气保护下,将化合物IV,命名为:1-(2-羟乙基)-2,3,3-三甲基-3H-吲哚-1-鎓溴化物(2g)和化合物V,命名为:(E)-4-异丙氧基-3-(1-烯丙基)苯甲醛(1.53g)溶于乙醇中,并滴加3滴甲基磺酸作为催化剂。回流8h,旋干溶剂,乙酸乙酯\正己烷混合洗旋干后的残余物,得橙黄色固体。
2)再将上述得到橙黄色固体溶于50mL的5%的氢氧化钾的水溶液中,用乙酸乙酯萃取(3x30mL),无水硫酸镁干燥,旋干,得黄色固体I。
1H NMR(400MHz,CDCl3)δ7.57(s,1H),7.33–7.27(m,1H),7.21(t,J=7.6Hz,1H),7.13(d,J=7.2Hz,1H),6.99(t,J=7.5Hz,1H),6.92–6.82(m,3H),6.75(d,J=15.9Hz,1H),6.31(dq,J=13.4,6.5Hz,1H),6.20(d,J=15.9Hz,1H),4.58(dq,J=11.6,5.8Hz,1H),3.91–3.45(m,5H),1.96(d,J=6.5Hz,3H),1.50(s,3H),1.40(d,J=6.0Hz,6H),1.22(s,3H).13C NMR(101MHz,CDCl3)δ154.58(s),150.70(s),139.89(s),131.99(s),129.05(s),128.40(s),127.55(s),126.39(s),126.08(s),125.75(s),124.89(s),123.47(s),122.41(s),121.65(s),114.33(s),112.03(s),110.07(s),70.99(s),63.51(s),50.13(s),47.92(s),28.47(s),28.10(s),22.21(s),20.35(s),18.96(s)
化合物1的合成路线
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂,用式(II)所示:
实施例2
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法,包括如下步骤:
氮气保护下,Grubbs II催化剂(III)(1.86g,2.2mmol)和氯化亚铜(0.220g,2.2mmol)和化合物I(1.16g,2.75mmol)溶于25mL二氯甲烷中,在搅拌下,加热回流30min,降温至室温,旋干,过色谱硅胶柱,向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质,再加入二氯甲烷洗脱得到1g绿色固体。
所述Grubbs II催化剂的结构见(III):
经检测,1H NMR(400MHz,CDCl3):δ16.54(s,1H),7.57(d,J=8.4Hz,1H),7.20–6.99(m,7H),6.86–6.69(m,3H),6.00(d,J=15.9Hz,1H),4.91(m,J=12.3,6.1Hz,1H),4.20(s,4H),3.89–3.36(m,4H),2.42(t,J=30.6Hz,18H),1.44(s,3H),1.29(d,J=5.9Hz,6H),1.18(s,3H). 13C NMR(101MHz,CDCl3):δ211.04,152.10,149.37,145.43,141.71,138.83,131.15,130.81,129.41,127.99,127.46,126.52,124.52,122.87,120.24,112.99,109.94,63.58,53.44,50.06,48.13,30.84,28.17,27.30,26.01,21.09,20.14.MS(ESI)m/z CalcdFor[C45H52ClN3O2Ru][M-2Cl+H]+ 803.2792,found 804.2892.Anal.Calcd.forC45H52Cl3N3O2Ru:C 61.74,H 6.10,N 4.80;Found:C 61.89,H 6.23,N 4.76.CCDC:1458091为吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)。
实施例3
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)(下面实施例中简称为催化剂II)在闭环交叉复分解反应中的应用
4-丙二酸二乙酯基环戊烯(化合物2)的合成:
在40℃条件下,将二烯丙基丙二酸二乙酯(化合物1)(24mg(0.1mmol)和0.875毫克(1mol%)催化剂II加入1mL的二氯甲烷,搅拌。反应7min,旋干反应溶剂后提纯产品,产率为90%,经核磁确定,1H NMR(400Hz,CDCl3):δ5.59(s,2H),4.18(q,J=7.1Hz,4H),3.00(s,4H),1.23(t,J=7.1Hz,6H).13C NMR(100MHz,CDCl3):δ172.16,127.77,61.46,58.80,40.80,13.98.产物是4-丙二酸二乙酯基环戊烯(化合物2)。
实施例4
1-(4-甲基苯磺酰基)-2,5-二氢-1H-吡咯(化合物4)的合成,操作同实施例3,反应原料之一为化合物3(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.72(dd,J=8.2,1.6Hz,2H),7.32(d,J=7.6Hz,2H),5.65(s,2H),4.11(d,J=2.1Hz,4H),2.42(d,J=1.8Hz,3H).13C NMR(100MHz,CDCl3):δ143.49,134.23,129.79,127.40,125.46,54.86,21.52.
实施例5
1-(甲苯-4-磺酰基)-2,5-二氢-3-甲基吡咯(化合物6)的合成,操作同实施例3,反应原料之一为化合物5(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.72(t,J=6.5Hz,2H),7.32(d,J=7.9Hz,2H),5.25(d,J=1.4Hz,1H),4.01(d,J=40.1Hz,4H),2.42(d,J=6.1Hz,3H),1.65(s,3H).13C NMR(100MHz, CDCl3):δ143.40,135.05,134.22,129.75,127.41,119.08,57.69,55.15,21.50,14.04.
实施例6
1-(甲苯-4-磺酰基)-2,3,6-三氢吡啶(化合物10)的合成,操作同实施例3,反应原料之一为化合物9(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.69(d,J=7.2Hz,2H),7.34(d,J=7.9Hz,2H),5.83–5.55(m,2H),3.59(d,J=1.9Hz,2H),3.27–3.11(m,2H),2.45(s,3H),2.28–2.14(m,2H).13CNMR(100MHz,CDCl3):δ143.52,133.39,129.64,127.69,125.07,122.77,44.79,42.66,25.28,21.52.
实施例7
1-(甲苯-4-磺酰基)-2,3,6,7-四氢-1H吖庚因(化合物12)的合成,操作同实施例3,反应原料之一为化合物11(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.68(d,J=8.1Hz,2H),7.31(d,J=8.0Hz,2H),5.81–5.71(m,2H),3.35–3.21(m,4H),2.42(s,3H),2.32(d,J=4.7Hz,4H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例8
2,5-二氢苯并恶庚英(化合物14)的合成,操作同实施例3,反应原料之一为化合物13(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.41–7.13(m,4H),6.07–5.90(m,1H),5.64–5.55(m,1H),4.72(dd,J=4.8,2.4Hz,2H),3.64(d,J=2.7Hz,2H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例9
4-甲基-2,5-二氢苯并恶庚英(化合物16)的合成,操作同实施例3,反应原料之一为化合物15(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.37–7.29(m,1H),7.26–7.12(m,3H),5.40(d,J=1.0Hz,1H),4.70(dd,J=3.2,1.6Hz,2H),3.60(s,2H),2.01(s,3H).13C NMR(100MHz,CDCl3):δ158.86,134.97,134.07,129.19,128.04,123.67,121.26,70.40,37.39,26.30.
实施例10
2,5-二氢-1H吡咯基苯基甲酮(化合物18)的合成,操作同实施例3,反应原料之一为化合物17(催化剂用量、反应时间及产率,见表1)
1H NMR(400MHz,CDCl3):δ7.21–7.09(m,2H),7.02(d,J=2.7Hz,3H),5.48(s,1H),5.34(d,J=1.5Hz,1H),4.04(s,2H),3.77(s,2H).13C NMR(100MHz,CDCl3):δ169.26,136.57,129.59,128.06,126.60,125.33,55.45,53.14.
实施例11
1-(甲苯-4-磺酰基)-2,5-二氢-3,4-二甲基吡咯(化合物8)的合成,操作同实施例3,反应原料之一为化合物7(催化剂用量、反应时间及产率,见表1)
在80℃条件下,将二烯丙基丙二酸二乙酯(279mg(1mmol)和0.875毫克(1mol%)催化剂II加入1mL的二氯甲烷,搅拌。反应7min,旋干反应溶剂后提纯产品,产率为90%,经核磁确定,1H NMR(400MHz,CDCl3):δ7.73(d,J=8.0Hz,2H),7.34(d,J=7.8Hz,2H),3.99(s,4H),2.44(s,3H),1.56(s,6H).13C NMR(100MHz,CDCl3):δ143.29,134.30,129.72,127.49,126.21,58.83,21.52,11.12.
实施例12
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)在交叉复分解反应中的应用
苯甲酸肉桂酯(化合物21)的合成(产率,见表1)
在40℃条件下,将苯甲酸烯丙酯(化合物19,16.2mg,0.1mmol)、苯乙烯(化合物20,20.8mg,0.2mmo)和0.875mg(1mol%)催化剂II加入1ml的二氯甲烷,搅拌,反应12min,旋干反应溶剂后提纯产品,产率为89%,经核磁确定1H NMR(400Hz,CDCl3):δ8.12(d,J=7.22Hz,2H),7.60(t,J=7.38Hz,2H),7.44-7.50(q,J=7.51Hz,2H),7.36(t,J=7.19Hz,1H),7.29(t,J=7.10Hz,1H),6.78(d,J=16.0Hz,4H),6.40-6.44(m,1H),5.02(dd,J=6.39Hz and J=0.97Hz,3H).
表1为催化剂II对不同底物催化活性测试实验a
表头及表中:
a此反应溶液浓度为0.1M(其中,化合物7底物浓度为1M);
b产率为分离产率;
c此反应在100℃的甲苯溶液中反应。
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Claims (4)
1.吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂,其特征是用式(II)所示:
2.权利要求1的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法,其特征是包括如下步骤:
氮气保护下,将Grubbs II催化剂(III)、氯化亚铜和化合物(I)溶于二氯甲烷中,在搅拌下,加热回流,降温至室温,旋干,过色谱硅胶柱,向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质,再加入二氯甲烷洗脱得到吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II);
反应式如下:
所述Grubbs II催化剂的结构见(III):
3.根据权利要求2所述的制备方法,其特征是所述Grubbs II催化剂(III),氯化亚铜和化合物(I)的摩尔比为1:1:1.25。
4.权利要求1的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中的应用。
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